Phase behaviour of binary systems of lactones in carbon dioxide

Experimental phase equilibrium data for binary systems involving ε-caprolactone, δ-hexalactone, and γ-caprolactone with carbon dioxide have been measured applying the synthetic method using a high-pressure, variable-volume view cell over the temperature range of (303 to 343) K and pressures up to 21 MPa. For the systems investigated, (vapour + liquid) (VLE), (liquid + liquid) (LLE), and (vapour + liquid + liquid) (VLLE) equilibrium were visually recorded. It was observed that an increase in temperature or in carbon dioxide concentration led to a pronounced raise in transition pressure values. The experimental results were modelled using the Peng–Robinson equation of state with the conventional quadratic mixing rule, affording a satisfactory representation of the experimental values.     

Phase behaviour of the ternary system {poly(ε-caprolactone) + carbon dioxide + dichloromethane}

Recently, production of biocompatible and biodegradable polymer microparticles has been a matter of growing interest in pharmaceutical and food areas such as drug or active compounds delivery. To conduct production of microparticles, polymeric particle coating, impregnation of active compounds in polymeric films, the knowledge of phase behaviour involving the biodegradable polymer in supercritical carbon dioxide in the presence of a modifier may be needed to allow developing new industrial applications. In this sense, the aim of this work was to investigate the phase behaviour of the ternary system formed by the biodegradable polymer poly(ε-caprolactone) in (carbon dioxide + dichloromethane). Experimental phase transition (bubble and cloud point) values were obtained by applying the static-synthetic method using a variable-volume view cell over the temperature range of (303 to 343) K and pressures up to 21 MPa, in the CO₂ overall composition range of (25–46) wt%, while polymer concentrations studied were (1, 3, 5, and 7) wt%. For the system investigated, depending on the polymer concentration, vapour–liquid, liquid–liquid, and vapour–liquid–liquid phase transitions were verified.     

Accuracy assessment of the linear Poisson–Boltzmann equation and reparametrization of the OBC generalized Born model for nucleic acids and nucleic acid–protein complexes

The generalized Born model in the Onufriev, Bashford, and Case (Onufriev et al., Proteins: Struct Funct Genet 2004, 55, 383) implementation has emerged as one of the best compromises between accuracy and speed of computation. For simulations of nucleic acids, however, a number of issues should be addressed: (1) the generalized Born model is based on a linear model and the linearization of the reference Poisson–Boltmann equation may be questioned for highly charged systems as nucleic acids; (2) although much attention has been given to potentials, solvation forces could be much less sensitive to linearization than the potentials; and (3) the accuracy of the Onufriev–Bashford–Case (OBC) model for nucleic acids depends on fine tuning of parameters. Here, we show that the linearization of the Poisson Boltzmann equation has mild effects on computed forces, and that with optimal choice of the OBC model parameters, solvation forces, essential for molecular dynamics simulations, agree well with those computed using the reference Poisson–Boltzmann model. © 2015 Wiley Periodicals, Inc.     

Phase behavior of (CO2 + methanol + lauric acid) system

In this study the phase equilibrium behaviors of the binary system (CO₂ + lauric acid) and the ternary system (CO₂ + methanol + lauric acid) were determined. The static synthetic method, using a variable-volume view cell, was employed to obtain the experimental data in the temperature range of (293 to 343) K and pressures up to 24 MPa. The mole fractions of carbon dioxide were varied according to the systems as follows: (0.7524 to 0.9955) for the binary system (CO₂ + lauric acid); (0.4616 to 0.9895) for the ternary system (CO₂ + methanol + lauric acid) with a methanol to lauric acid molar ratio of (2:1); and (0.3414 to 0.9182) for the system (CO₂ + methanol + lauric acid) with a methanol to lauric acid molar ratio of (6:1). For these systems (vapor + liquid), (liquid + liquid), (vapor + liquid + liquid), and (solid + fluid) transitions were observed. The phase equilibrium data obtained for the systems were modeled using the Peng–Robinson equation of state with the classical van der Waals mixing rule with a satisfactory correlation between experimental and calculated values.     

Synthesis and application of imprinted polyvinylimidazole-silica hybrid copolymer for Pb determination by flow-injection thermospray flame furnace atomic absorption spectrometry

A novel ion imprinted polyvinylimidazole-silica hybrid copolymer (IIHC) was synthesized and used as a selective solid sorbent for Pb²⁺ ions preconcentration using an on-line solid phase extraction (SPE) system coupled to TS-FF-AAS. The ionic hybrid sorbent was prepared using 1-vinylimidazole and 3-(trimethoxysilyl)propylmethacrylate as monomers, Pb²⁺ ions as template, tetraethoxysilane as reticulating agent and 2,2′-azobis-isobutyronitrile as initiator. The best on-line SPE conditions concerning sorption behavior, including sample pH (6.46), buffer concentration (9.0 mmol L⁻¹), eluent (HNO₃) concentration (0.5 mol L⁻¹) and preconcentration flow rate (4.0 mL min⁻¹), were optimized by means of full factorial design and Doehlert matrix. The analytical curve ranged from 2.5 to 65.0 μg L⁻¹ (r = 0.999) with limit of detection of 0.75 μg L⁻¹; the precision (repeatability) calculated as relative standard deviation (n = 10) was 5.0 and 3.6% for Pb²⁺ concentration of 10.0 and 60.0 μg L⁻¹, respectively. From on-line breakthrough curve, column capacity was 3.5 mg g⁻¹. Preconcentration factor (PF), consumptive index (CI) and concentration efficiency (CE) were 128.0, 0.16 mL and 25.6 min⁻¹, respectively. The selective performance of the sorbent, based on relative selectivity coefficient, was compared to NIC (non imprinted copolymer) for the binary mixture Pb²⁺/Cd²⁺, Pb²⁺/Cu²⁺ and Pb²⁺/Zn²⁺. The results showed that ion imprinted polyvinylimidazole-silica hybrid polymer had higher selectivity for Pb²⁺ than NIC at 64.9, 16.0 and 8.8 folds. The developed method was successfully applied for highly sensitive and selective Pb²⁺ determination in different kinds of water samples, parenteral solutions and urine. Accuracy was also assessed by analyzing certified reference fish protein (DORM-3) and marine sediment (MESS-3 and PACS-2) with satisfactory results.     

Artificial neural network for aspect ratio prediction of lignocellulosic micro/nanofibers

Cellulose - In this work a wide sample analysis, under similar conditions, has been carried out and a calibration strategy based on a careful selection of input variables combined with sensitivity...     

Phase equilibrium measurements of ternary systems formed by linoleic and linolenic acids in carbon dioxide/ethanol mixtures

This work reports phase equilibrium measurements for the ternary systems linoleic (acid + CO₂ + ethanol) and (linolenic acid + CO₂ + ethanol). The fatty acids present in the ternary systems were selected based on composition of banana peel oil extracted by supercritical CO₂ at 20 MPa and 313 K. The motivation of this research relies on the fact that these unsaturated fatty acids are recognized to play an important role in lowering blood pressure and serum cholesterol and because they are present in high concentrations in banana peel extract. Besides that, equilibrium data of these compounds are scarce in literature. The phase equilibrium experiments were performed using a high-pressure variable-volume view cell over the temperature range of (303 to 343) K and pressures up to 19 MPa. For both systems, only vapour–liquid phase transitions were visually recorded for all data measured.     

Kinetics of ultrasound-assisted lipase-catalyzed glycerolysis of olive oil in solvent-free system

This work reports experimental kinetic data of solvent-free glycerolysis of olive oil using a commercial immobilized lipase (Novozym 435) under the influence of ultrasound irradiation. The experiments were performed in a mechanically stirred reactor under ultrasound irradiation, evaluating the effects of temperature (50-70 °C), enzyme concentration (2.5-10 wt%) and glycerol to oil molar ratio (0.8:1-3:1). Results show that ultrasound-assisted lipase-catalyzed glycerolysis might be a potential alternative route to conventional methods, as high contents of reaction products, especially monoglycerides, were achieved at mild irradiation power supply (∼130 W) and temperature, in a relatively short reaction time (2 h) and low enzyme content (7.5 wt%). To completeness, two simplified kinetic modeling approaches, based on the ordered-sequential bi bi mechanism and reaction stoichiometry, were employed to represent the experimental data, thus allowing a better understanding of the reaction kinetics.